TW520379B - Dip forming latex and dip-formed article - Google Patents

Abstract

Provided is a dip-formed article and a latex for dip forming said article which will not cause protein allergy, has soft feeling and is excellent in mechanical strength. In a copolymer latex obtained by polymerizing 10 to 90 wt% of a conjugated diene monomer, 0.1 to 20 wt% of an ethylenically unsaturated monomer, and 10 to 89.9 wt% of other ethylenically unsaturated monomers which can be copolymerized with these monomers, the total amount of the acid groups bound or adhered to the surface of the copolymer constituting the latex and the acid groups presented in the aqueous phase of said copolymer, converted and calculated as hydrochloric acid equivalent, is 0.1 to 2 meq of latex per gram of the copolymer, whereby a dip formed article having excellent property is obtained.

Description

520379 A7 B7 五、發明説明（) 【發明領域】 本發明係有關一種浸漬模製物及浸漬模製用乳膠，更詳言 之，係有關一種不會引起蛋白過敏、質感柔軟、且機械強度 優異的浸漬模製物以及爲製得該浸漬模製物之浸漬模製用 乳膠。 【先前技術】 以往，橡膠手套係使用在天然橡膠乳膠中配合有加硫劑 之硫等的組成物予以浸漬模製者。然而，最近由於天然橡膠 乳膠中所含的天然蛋白質於接近人體之皮膚時，會引起過 敏反應且會引起發疹、發癢等情形。 另外，亦有進行由在丙烯酸-丙烯膪-丁二烯共聚物乳膠 等羧酸改性的腈系共聚物乳膠中配合有交聯劑之氧化鋅的 組成物予以浸漬模製。如此所得的浸漬模製物由於具有優異 的耐油性、高機械強度，雖適合於使用有機溶劑之作業場所 ，惟有質感硬的缺點。 此處，爲改善此點之方法，提案有使天然橡膠乳膠與羧 酸改性的腈系共聚物乳膠交互重疊予以浸漬模製的方法、或 使用混合羧酸改性的膪系共聚物乳膠與羧酸改性的合成順 式-1 , 4 -聚異戊二烯橡膠乳膠的方法（日本特開昭53-1 0 1 0 3 6號公報）等。然而，以前者之方法時由於使用天然橡 膠乳膠、會有蛋白過敏的問題，而以後者的方法時由於使用 不同種的乳膠致使工程複雜化、會有降低生產性的.問題。 【發明解決之課題】 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)520379 A7 B7 V. Description of the invention (Field of invention) The present invention relates to an impregnated molded article and latex for impregnated molding. More specifically, it relates to a kind that does not cause protein allergy, has a soft texture, and has excellent mechanical strength. And a latex for dipping molding to obtain the dipping molding. [Prior Art] Conventionally, rubber gloves are impregnated with a composition in which natural sulfur latex is compounded with sulfur and the like. However, recently, natural proteins contained in natural rubber latex can cause allergic reactions and cause rashes, itching, etc. when they approach human skin. In addition, a composition in which zinc oxide is mixed with a cross-linking agent in a carboxylic acid-modified nitrile copolymer latex such as an acrylic-acrylic acid-acrylic acid-butadiene copolymer latex is also impregnated and molded. The impregnated molding obtained in this way has excellent oil resistance and high mechanical strength, and although it is suitable for a work place using an organic solvent, it has the disadvantage of being hard in texture. Here, in order to improve this point, a method is proposed in which a natural rubber latex and a carboxylic acid-modified nitrile copolymer latex are alternately overlapped and molded, or a mixed carboxylic acid-modified fluorene-based copolymer latex and Method for synthesizing cis-1,4-polyisoprene rubber latex modified by carboxylic acid (Japanese Patent Application Laid-Open No. 53-1 0 106) and the like. However, in the former method, there is a problem of protein allergy due to the use of natural rubber latex, while in the latter method, the use of different types of latex complicates engineering and reduces productivity. [Problems to be solved by the invention] This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

經濟部智慧財產局員工消費合作社印製 520379 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（） 有鑑於上述之課題，本發明目的係提供一種不會引起蛋 白過敏、質感柔軟、機械強度優異的浸漬模製物以及爲製得 該浸漬模製物之浸漬模製用乳膠。 【爲解決課題之手段】 本發明人等爲達成本發明目的，再三深入硏究的結果，發 現構成乳膠之共聚物表面的酸基量與該共聚物乳膠之水相 中酸基量會影響浸漬模製物之質感，基於該見解遂而完成 本發明。 如此，本發明係提供一種浸漬模製用乳膠，其係於使由 10〜90重量％共軛二烯單體、0 · 1〜20重量％乙烯性不飽和 酸單體、及1 〇〜89 · 9重量％可與此等共聚合之其他乙烯性 不飽和單體所成的單體予以聚合製得的共聚物之乳膠中，其 特徵爲在構成乳膠之共聚物表面上結合或吸附的酸基量與 該共聚物乳膠於水相中酸基量之合計以鹽酸當量換算爲1 g 共聚物中具0.1〜2毫當量。 而且，本發明亦提供使上述之浸漬模製用乳膠予以浸漬 模製所成的浸漬模製物。 【發明之實施形態】 於下述中詳細地說明本發明。 本發明之浸漬模製用乳膠可藉由使由10〜90重量％共軛 二烯單體、0. 1〜20重量％乙烯性不飽和酸單體、及10〜 8 9 . 9重量％可與此等共聚合之其他乙烯性不飽和單體所成 的單體聚合製得。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 520379 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () In view of the above problems, the purpose of the present invention is to provide a protein that does not cause protein allergy, has a soft texture, An impregnated molded article having excellent mechanical strength and a latex for impregnated molding to obtain the impregnated molded article. [Means to solve the problem] The inventors have repeatedly studied to achieve the purpose of the invention, and found that the amount of acid groups on the surface of the copolymer constituting the latex and the amount of acid groups in the aqueous phase of the copolymer latex affect the impregnation. Based on this knowledge, the texture of the molded object has completed the present invention. As described above, the present invention provides a latex for dip molding, which is composed of 10 to 90% by weight of a conjugated diene monomer, 0.1 to 20% by weight of an ethylenically unsaturated acid monomer, and 10 to 89%. 9% by weight of a copolymer latex copolymerized with other ethylenically unsaturated monomers made from these copolymerized monomers, which is characterized by an acid bound or adsorbed on the surface of the copolymer constituting the latex The total of the base amount and the acid group amount of the copolymer latex in the aqueous phase is converted into 1 g of the copolymer in terms of hydrochloric acid equivalent and has 0.1 to 2 milliequivalents. The present invention also provides an impregnated molded article obtained by impregnating and molding the above-mentioned latex for impregnated molding. [Embodiments of the invention] The present invention will be described in detail below. The latex for dipping molding of the present invention can be made by 10 to 90% by weight of a conjugated diene monomer, 0.1 to 20% by weight of an ethylenically unsaturated acid monomer, and 10 to 89.9% by weight of Monomers made by copolymerizing other ethylenically unsaturated monomers are prepared by polymerization. This paper size applies to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page)

經濟部智慧財產局員工消費合作社印製 520379 A7 B7 五、發明説明（） 所使用的共軛二烯單體沒有特別的限制，具體例如1，3 -丁二烯、異戊二烯、2, 3-二甲基-1，3-丁二烯、2-乙基-1，3-丁二烯、1,3 -戊二烯及氯化戊二烯等。此等之共軛二烯單 體可單獨使用，亦可二種以上組合使用。於上述中，以1，3 -丁二烯或異戊二烯較佳。該單體之使用量爲全部單體之1〇 〜90重量％、較佳者爲20〜80重量％、更佳者爲25〜75重 量％。若少於1 0重量％時無法得到做爲手套用之質感，而若 多於9 0重量％時會降低拉伸強度及斷裂強度、且無法得到做 爲手套用之保形性。 共軛二烯單體之使用量係視與其倂用的其他乙烯性不飽 和單體之種類而定，在上述範圍內適當地選擇，惟使用乙 烯性不飽和腈單體做爲其他乙烯性不飽和單體時，較佳者爲 單體之3 0〜90重量％、更佳者爲3 5〜8 0重量％。而且， 使用芳香族乙烯單體做爲其他乙烯性不飽和單體時，爲單體 之10〜90重量％、較佳者爲2 0〜8 0重量％。爲上述任一 種時，若共軛二烯單體之量過少時會使浸漬模製物之質感變 硬，反之若過多時會使拉伸強度及斷裂強度降低。 乙烯性不飽和酸單體爲含有羧基、磺酸基、酸酐基等酸性 基之乙烯性不飽和單體即可，沒有特別的限制。其具體例爲 丙烯酸、甲基丙烯酸等之乙烯性不飽和單羧酸單體；衣康酸 、馬來酸、富馬酸、戊烯三羧酸等之乙烯性不飽和多元羧酸 單體；富馬酸-丁酯、馬來酸-丁酯、馬來酸-2 —羥基丙 酯等之乙烯性不飽和多元羧酸之部分酯單體；馬來酸酐、檸 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） —---------^------訂 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員Η消費合作社印製 520379 Μ Β7 五、發明説明（） 康酸酐等之多元羧酸酐；苯乙烯磺酸、乙烯基磺酸、甲基乙 烯基磺酸、（甲基）烯丙基磺酸、（曱基）丙烯酸一 2 -磺 酸乙酯、2 -丙烯醯胺- 2 -羥基丙烷磺酸等之乙烯性不飽 和磺酸單體；（甲基）丙烯酸一 3 -氯—2 -磷酸丙酯、（ 甲基）丙烯酸一 2 -磷酸乙酯、3 -芳氧基一 2 —羥基丙烷 磷酸等之乙烯性不飽和磷酸單體；等。此等之單體亦可使用 做爲鹼金屬鹽或銨鹽。而且，此等之單體可單獨使用，亦可 二種以上組合使用。於上述之單體中，就浸漬模製物之質感 與拉伸強度之平衡點而言以乙烯性不飽和單羧酸單體較佳 ，更佳者爲曱基丙烯酸。 乙烯性不飽和酸單體之使用量係爲全部單體之0 . 1〜2 0重量％、較佳者爲1〜1 5重量％、更佳者爲2〜1 0重量％ 。若少於0 . 1重量％時會降低浸漬模製物之拉伸強度，反 之若大於2 0重量％時會降低浸漬模製物之斷裂強度且會使 質感變硬。 其他乙烯性不飽和單體可使用乙烯性不飽和腈單體、芳香 族乙烯單體、乙烯性不飽和酸衍生物系單體、交聯性單體等 。此等單體之種類及使用量，就考慮目的之浸漬模製物所要 求的質感、耐油性、機械強度等各種特性予以適當地決定， 惟其中就具優異耐油性而言以乙烯性不飽和腈單體較佳。 對於乙烯性不飽和腈單體沒有特別的限制。其具體例如丙 烯腈、甲基丙嫌膪、富馬膪、α -氯丙烯腈、α —氰基乙基 丙烯腈等，其中以丙烯腈較佳。乙烯性不飽合腈單體之使用 -6 - ^紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐1 (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 520379 A7 B7 V. Description of the invention () There is no particular limitation on the conjugated diene monomers used, such as 1,3-butadiene, isoprene, 2, 3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, pentadiene chloride, and the like. These conjugated diene monomers may be used alone or in combination of two or more kinds. Among the above, 1,3-butadiene or isoprene is preferred. The monomer is used in an amount of 10 to 90% by weight, preferably 20 to 80% by weight, and more preferably 25 to 75% by weight. If it is less than 10% by weight, the texture as a glove cannot be obtained, and if it is more than 90% by weight, the tensile strength and the breaking strength are reduced, and the shape retention property as a glove cannot be obtained. The amount of conjugated diene monomer used depends on the type of other ethylenically unsaturated monomers used in it. It is appropriately selected within the above range, but the ethylenically unsaturated nitrile monomer is used as the other ethylenically unsaturated monomer. When the monomer is saturated, it is preferably 30 to 90% by weight of the monomer, and more preferably 35 to 80% by weight. When an aromatic vinyl monomer is used as the other ethylenically unsaturated monomer, it is 10 to 90% by weight of the monomer, preferably 20 to 80% by weight. In any of the above cases, if the amount of the conjugated diene monomer is too small, the texture of the impregnated molded article will be hardened, and if it is too large, the tensile strength and the breaking strength will be reduced. The ethylenically unsaturated acid monomer is not particularly limited as long as it is an ethylenically unsaturated monomer containing an acidic group such as a carboxyl group, a sulfonic acid group, or an acid anhydride group. Specific examples thereof include ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid and methacrylic acid; ethylenically unsaturated polycarboxylic acid monomers such as itaconic acid, maleic acid, fumaric acid, and pentenetricarboxylic acid; Partial ester monomers of ethylenically unsaturated polycarboxylic acids such as fumaric acid-butyl ester, maleic acid-butyl ester, and maleic acid 2-hydroxypropyl ester; maleic anhydride and lemon (CNS) A4 specification (210X297 mm) —--------- ^ ------ Order (Please read the precautions on the back before filling this page) Printed by a member of the Intellectual Property Bureau of the Ministry of Economic Affairs and a Consumer Cooperative 520379 Μ B7 V. Description of the invention () Polycarboxylic acid anhydrides such as formic acid anhydride; styrene sulfonic acid, vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, (fluorenyl) acrylic acid Ethylene unsaturated sulfonic acid monomers such as ethyl 2-sulfonate, 2-propenylamine 2-hydroxypropanesulfonic acid; (meth) acrylic acid 3-chloro-2-propyl phosphate, (methyl ) Ethylene unsaturated phosphoric acid monomers such as ethyl 2-phosphate, 3-aryloxy 2-hydroxypropane phosphate, etc .; etc. These monomers can also be used as alkali metal or ammonium salts. These monomers may be used alone or in combination of two or more kinds. Among the above-mentioned monomers, in terms of the balance between the texture and tensile strength of the impregnated molding, an ethylenically unsaturated monocarboxylic acid monomer is preferred, and the more preferred is fluorenyl acrylic acid. The amount of the ethylenically unsaturated acid monomer used is 0.1 to 20% by weight of the total monomers, preferably 1 to 15% by weight, and more preferably 2 to 10% by weight. If it is less than 0.1% by weight, the tensile strength of the impregnated molded article will be reduced, and if it is more than 20% by weight, the breaking strength of the impregnated molded article will be reduced and the texture will be hardened. Examples of other ethylenically unsaturated monomers include ethylenically unsaturated nitrile monomers, aromatic vinyl monomers, ethylenically unsaturated acid derivative-based monomers, and crosslinkable monomers. The type and amount of these monomers are appropriately determined in consideration of various properties such as texture, oil resistance, and mechanical strength required for the purpose of the impregnated molded article, but among them, ethylenic unsaturated is used for excellent oil resistance. Nitrile monomers are preferred. There are no particular restrictions on the ethylenically unsaturated nitrile monomer. Specific examples thereof include acrylonitrile, methacrylomethane, fumaran, α-chloroacrylonitrile, α-cyanoethylacrylonitrile, and the like, among which acrylonitrile is preferred. Use of ethylenically unsaturated nitrile monomers -6-^ Paper size applies to Chinese National Standard (CNS) Α4 specification (210 × 297 mm 1 (please read the precautions on the back before filling this page)

經濟部智慧財產局員工消費合作社印製 520379 A7 — _B7 五、發明説明（） 量視目的之浸漬模製物要求的特性而定，較佳者爲全部單體 之9〜5 〇重量％、更佳者爲2 〇〜4 5重量％。若少於該量 時浸漬模製物之耐油性不佳，而若過多時會使浸漬模製物 之質感變硬。 芳香族乙烯單體之具體例如有苯乙烯、甲基苯乙烯、乙烯 基甲苯、氯化苯乙烯、羥基甲基苯乙烯等，其中以苯乙烯較 佳。芳香族乙烯單體之使用量係視目的之手套要求的特性予 以決定，惟通常爲全部單體之1 0〜8 9 · 9重量％、較佳者 爲20〜80重量，若少於該量時浸漬模製物之質感過軟，而 若過多時會使浸漬模製物之質感變硬。 乙烯性不飽和酸衍生物系單體之具體例，如乙烯性不飽 酸酯單體、乙烯性不飽和酸醯胺單體等。乙烯性不飽和酸酯 單體係爲乙烯性多元不飽和酸與具有鹵素等取代基之各種 醇類的酯類。此等之具體例如（甲基）丙烯酸甲酯、（甲基 )丙烯酸乙酯、（曱基）丙烯酸丙酯、（甲基）丙烯酸丁酯 、（甲基）丙烯酸一2 —乙基己酯、（甲基）丙烯酸三氟乙 酯、（甲基）丙烯酸四氟丙酯、（甲基）丙烯酸甲氧基甲酯 、（甲基）丙烯酸乙氧基乙酯、（甲基）丙烯酸甲氧基乙氧 基乙酯、（甲基）丙嫌酸氰基曱酯、（甲基）丙燒酸2 —氰 基乙酯、（甲基）丙烯酸1—氰基丙酯、（甲基）丙烯酸2 —乙基一 6 —氰基己酯、（甲基）丙烯酸3 —氰基丙酯、（ 甲基）丙烯酸羥基乙酯、（甲基）丙烯酸羥基丙酯、（甲基 )丙烯酸環氧丙酯、（甲基）丙烯酸—N，N -二甲基胺基 本紙張尺度適用中國國家標準（CNS )八4規格（21〇Χ297公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 520379 A7 — _B7 V. Description of the invention () The amount depends on the characteristics required for the purpose of the impregnated molding, preferably 9-95% by weight of all monomers, more The best is 20 to 45% by weight. If it is less than this amount, the oil resistance of the impregnated molded article is not good, and if it is too large, the texture of the impregnated molded article becomes hard. Specific examples of the aromatic vinyl monomer include styrene, methylstyrene, vinyltoluene, chlorinated styrene, and hydroxymethylstyrene. Among them, styrene is preferred. The amount of aromatic vinyl monomer used is determined according to the characteristics required by the gloves used for the purpose, but it is usually 10 to 89% by weight of the total monomers, preferably 20 to 80% by weight, and if less than this amount The texture of the dip-molded article is too soft when it is too large, and the texture of the dip-molded article is hardened if too much. Specific examples of the ethylenically unsaturated acid derivative-based monomers include ethylenically unsaturated acid ester monomers, ethylenically unsaturated acid amidine monomers, and the like. Ethylene unsaturated esters Monoesters are esters of ethylenic polyunsaturated acids and various alcohols having substituents such as halogens. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (fluorenyl) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, methoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxy (meth) acrylate Ethoxyethyl, (meth) propanoic acid cyanoacetate, (meth) propionic acid 2-cyanoethyl ester, (meth) acrylic acid 1-cyanopropyl ester, (meth) acrylic acid 2 —Ethyl-6—cyanohexyl ester, 3-Cyanopropyl (meth) acrylate, Hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate, Glycidyl (meth) acrylate (Basic paper size of (meth) acrylic acid-N, N-dimethylamine) is applicable to China National Standard (CNS) 84 (21 × 297 mm) (Please read the precautions on the back before filling this page)

520379 A7 B7 五、發明説明（） 乙酯等之（甲基）丙烯酸酯；馬來酸二丁酯、富馬酸二丁酯 、馬來酸二乙酯等之多元羧酸酯；等。 乙烯性不飽和酸醯胺單體之具體例，如（甲基）丙烯酸醯 胺、N —羥甲基（甲基）丙烯酸醯胺、n，N —二羥甲基（ 甲基）丙烯酸醯胺、N —甲氧基甲基（甲基）丙烯酸醯胺、 N -丙氧基甲基（甲基）丙烯酸醯胺等之（甲基）丙烯酸醯 胺系單體等。 交聯性單體例如有二乙烯苯等之共軛二乙烯化合物；聚乙 二醇二（甲基）丙烯酸酯、聚丙二醇二（甲基）丙烯酸酯、 三羥甲基丙烷三（甲基）丙烯酸酯、季戊四醇（甲基）丙烯 酸酯等聚（甲基）丙烯酸酯化合物等。 本發明之浸漬模製用乳膠係在構成乳膠之共聚物表面上 結合或吸附的酸基量（以下稱爲「表面酸基量」）與該共聚 物乳膠於水相中酸基量（以下稱爲「水相酸基量」）之合計 (以下稱爲「總酸基量」），以鹽酸當量換算爲丨g共聚物中 具0.1〜2毫當量、較佳者爲〇.1 5〜1 .8毫當量。若總 酸基量少於0 . 1毫當量時做爲手套時交聯性不充分而使斷 裂強度變弱、且乳膠之膠體安定性不足，故於配合交聯劑時 會產生凝固物。而若多於2毫當量時，親水成分過多、在手 套浸漬於水中時容易使強度降低。 爲使乳膠之總酸基量控制於上述範圍內的方法沒有特別 的限制，通常藉由調整聚合時所使用的乙烯性不飽和酸單體 之種類、量或對聚合反應系之添加時期等予以進行。此外， 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇><297公釐） (請先閲讀背面之注意事項再填寫本頁)520379 A7 B7 V. Description of the invention () (meth) acrylates such as ethyl esters; polybutyl carboxylates such as dibutyl maleate, dibutyl fumarate, diethyl maleate, etc .; Specific examples of ethylenically unsaturated acid ammonium monomers, such as ammonium (meth) acrylate, ammonium N-methylol (meth) acrylate, and ammonium n, N-dimethylol (meth) acrylate , (Meth) acrylamide-based monomers such as N-methoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamine, and the like. Examples of the crosslinkable monomer include conjugated diethylene compounds such as divinylbenzene; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and trimethylolpropane tri (methyl) Poly (meth) acrylate compounds such as acrylate and pentaerythritol (meth) acrylate. The latex for dipping molding of the present invention is the amount of acid groups (hereinafter referred to as "surface acid groups") bound or adsorbed on the surface of the copolymer constituting the latex and the amount of acid groups (hereinafter referred to as "surface acid groups") of the copolymer latex in the water phase. Is the total amount of "acid groups in the aqueous phase") (hereinafter referred to as "total acid groups"), converted to hydrochloric acid equivalent to 0.1 to 2 milli-equivalents in the copolymer, preferably 0.1 to 5 .8 milliequivalents. If the total acid group content is less than 0.1 milliequivalents, the crosslinkability will be insufficient when used as gloves, and the breaking strength will be weakened, and the colloidal stability of the latex will be insufficient. Therefore, coagulum will be produced when the crosslinker is blended. On the other hand, if it is more than 2 milliequivalents, there is too much hydrophilic component, and the strength is liable to decrease when the glove is immersed in water. In order to control the total acid group amount of the latex within the above range, there is no particular limitation. Generally, it is adjusted by adjusting the type and amount of the ethylenically unsaturated acid monomer used in the polymerization or the addition period of the polymerization reaction system. get on. In addition, this paper size applies the Chinese National Standard (CNS) A4 specification (21〇 > < 297mm) (Please read the precautions on the back before filling this page)

、1T 經濟部智慧財產局員工消費合作社印製 520379 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（） 亦可倂用調整乳化劑或聚合啓始劑之種類或量、聚合系之P Η質等方法。 本發明之浸漬模製用乳膠係爲以下述式（1 )所定義的具化 學安定性指數CS質， Κ 5% S CS2 値、CS1 値 S 3 · 0% (1) CS1値：在100ml燒杯中各加入30ml之0.1重量％濃度不 同的NaCl溶液，於其中滴入1滴（約0. 2 cm3)固成分濃度爲 5重量％之乳膠時乳膠凝固之最小濃度。 CS2値：在100ml燒杯中各加入30ml之0.1重量％、濃度 不同的NaCl溶液，於其中滴入1滴（約0.2 cm3)固成分濃度 爲4 5重量％之乳膠時乳膠凝固之最小濃度。 CS2値變小時，乳膠之化學安定性降低、於配合氧化鋅、 硫分散液等時易產生凝固物，且浸漬模製性不佳致使膜厚 不均勻。而且，CS 1値變大時，化學安定性變高、膜之生成 性不佳、於浸漬後模具上升時配合液不會凝固而垂下、致使 膜厚不均勻。 控制乳膠之化學安定性的方法沒有特別的限制，例如可 控制單體混合物中之乙烯性不飽和酸單體、單體混合物聚合 時之乳化劑量及所得的共聚物乳膠之pH等。 本發明浸漬模製用乳膠，通常以常法之聚合乳化法製造 。乳化聚合之溫度通常爲0〜1 〇〇 °C，惟在45 t以下進行 時可容易地製得機械強度、質感優異的浸漬模製物。而且， 單體混合物之添加方法沒有特別的限制，可採用一起將單 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） (請先閲讀背面之注意事項再填寫本頁)1T printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 520379 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () It is also possible to adjust the type or amount of emulsifier or polymerization initiator, and the polymerization system P and other methods. The latex system for dipping molding of the present invention is a chemical substance having a chemical stability index CS as defined by the following formula (1), κ 5% S CS2 値, CS1 値 S 3 · 0% (1) CS1 値: in a 100ml beaker 30 ml of 0.1% by weight NaCl solutions with different concentrations were added to each, and one drop (about 0.2 cm3) of the latex having a solid content concentration of 5% by weight was added dropwise to the minimum concentration of latex coagulation. CS2 値: 30 ml of 0.1% by weight NaCl solutions of different concentrations are added to 100ml beakers, and 1 drop (about 0.2 cm3) of the latex with a solid content concentration of 45% by weight is added to the minimum concentration of latex coagulation. When CS2 becomes smaller, the chemical stability of the latex decreases, and coagulum is easily generated when zinc oxide, sulfur dispersion is mixed, etc., and the impregnability of the dip moldability is poor, resulting in uneven film thickness. When CS 1CS becomes larger, the chemical stability becomes higher, and the film formation becomes poor. When the mold rises after immersion, the compounding liquid does not solidify and sags, resulting in uneven film thickness. The method for controlling the chemical stability of the latex is not particularly limited, for example, the ethylenically unsaturated acid monomer in the monomer mixture, the emulsifying amount during the polymerization of the monomer mixture, and the pH of the obtained copolymer latex can be controlled. The latex for dip molding of the present invention is usually produced by a conventional polymerization emulsification method. The temperature of the emulsion polymerization is usually 0 to 100 ° C. However, when the temperature is 45 t or less, an impregnated molded article having excellent mechanical strength and excellent texture can be easily obtained. Moreover, there is no particular limitation on the method of adding the monomer mixture. The size of the paper can be applied to the Chinese National Standard (CNS) A4 (210 X297 mm) (please read the precautions on the back before filling this page)

520379 A7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明（） 體混合物加入聚合反應器中的方法 '連續將單體混合物供應 聚合反應器的方法、將部分單體混合物加入聚合反應器中、 再將殘餘的單體連續供應給聚合反應器之方法等。 聚合時所使用的聚合啓始劑沒有特別的限制。具體例如過 硫酸鈉、過硫酸鉀、過硫酸銨、過磷酸鉀、過氧化氫等之無 機過氧化物；二異丙苯氫化過氧化物、異丙苯氫化過氧化物 、第3 -丁基氫化過氧化物、1，1，3,3 -四甲基丁基氫化過氧 化物、2，5 -二甲基己烷· 2，5 -二氫化過氧化物、二-第3 - 丁 基過氧化物、二-α -異丙苯過氧化物、乙醯基過氧化物、異 丁醯基過氧化物、苯醯基過氧化物等之有機過氧化物；偶氮 雙異丁睛、偶氮雙-2, 4 -二甲基戊睛、偶氮雙異丁酸甲酯等 。此等之聚合啓始劑可各單獨使用或二種以上倂用。過氧化 物啓始劑可使乳膠安定、製造，而且，可得機械強度高、 質感柔軟之浸漬模製物係爲企求。啓始劑之使用量視其種類 稍有不同，對單體混合物而言以0.01〜0.6重量％較佳。 此外，可組合過氧化物啓始劑與還原劑做爲氧化還原系 聚合啓始劑使用。還原劑之具體例例如有氧化鐵、萘酸銅 等之還原狀態之含金屬離子之化合物；甲烷磺酸鈉等之磺酸 化合物；二甲基睛等之胺化合物；等。還原劑之使用量視其 種類而有所不同，對1重量份過氧化物而言以0.03〜10重 量份較佳。 於此等啓始劑之中以組合過氧化物啓始劑與還原劑之氧 化還原系聚合啓始劑更佳。 -1 0- ------： ί.. (請先閱讀背面之注意事項再填寫本頁) -----^-訂 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 520379 A7 B7 五、發明説明（） 聚合所使用的乳化劑沒有特別的限制，例如聚氧化乙烯 烷醚、聚氧化乙烯烷基苯醚、聚氧化乙烯烷酯、聚氧化乙烯 山梨糖醇烷醚等之非離子性乳化劑；肉豆蔻酸、棕侶酸、油 酸、亞油酸之脂肪酸及其鹽、高級醇硫酸酯、烷基磺基琥珀 酸、烷基苯磺酸鹽、脂肪族磺酸鹽等之陰離子性乳化劑；三 甲基銨氯化物、二烷基銨氯化物等之銨氯化物或苯甲銨鹽及 四級錢鹽等之陽離子性乳化劑；α，/3 -不飽和羧酸之磺酸酯 、α，0 -不飽和羧酸之硫酸酯、磺基烷基芳香酯等之共聚性 乳化劑等。尤以使用陰離子性乳化劑或非離子性乳化劑爲宜 。此等之乳化劑可單獨或二種以上組合使用，其使用量通 常對單體混合物而言爲0 . 1〜9重量％。 而且於聚合時，視其所需可使用分子量調整劑、粒徑調整 劑、抗老化劑、螯合劑、氧捕捉劑等之聚合副資材。 聚合通常在轉化率90%以上、較佳者爲95%以上、更佳者 爲99%以上進行。所得的乳膠之粒徑通常爲0 . 07〜0 . 3 // m 、較佳者爲0 . 08〜0 . 2 # m。若粒徑過小時，乳膠之黏度過 高、不易處理，且會使配合安定性降低。反之，過高時浸漬 模製物之成膜性不佳。 本發明之浸漬模製用乳膠係以含有具游離基連鏈禁止作 用之苯酚系化合物做爲抗老化劑較佳。苯酚系化合物對浸漬 模製物而言爲非污染性、臭味小、且即使於後工程中使浸漬 模製物氯化處理時仍不會引起變粉紅色的問題（耐變粉紅色 性優異）。而且，該氯化處理係爲解決使如手套之浸漬模製 -1 1 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁520379 A7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () Method for adding a monomer mixture to a polymerization reactor 'continuously supplying a monomer mixture to the polymerization reactor, adding a part of the monomer mixture to the polymerization reactor A method of continuously supplying residual monomers to a polymerization reactor. The polymerization initiator used in the polymerization is not particularly limited. Specific examples include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide, and the like; dicumyl hydroperoxide, cumene hydroperoxide, and 3-butyl Hydrogen peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane · 2,5-dihydroperoxide, di-3rd-butyl Organic peroxides such as peroxides, di-α-cumene peroxides, acetamyl peroxide, isobutylammonium peroxide, phenylammonium peroxide, etc .; azobisisobutylimide, azo Bis-2,4-dimethylpentane, methyl azobisisobutyrate, etc. These polymerization initiators can be used alone or in combination of two or more kinds. Peroxide initiators can stabilize and manufacture latex, and obtain impregnated molding systems with high mechanical strength and soft texture. The amount of the initiator used varies slightly depending on the type, and it is preferably 0.01 to 0.6% by weight for the monomer mixture. In addition, a peroxide initiator and a reducing agent may be used as a redox polymerization initiator. Specific examples of the reducing agent include metal ion-containing compounds in a reduced state such as iron oxide and copper naphthalate; sulfonic acid compounds such as sodium methanesulfonate; amine compounds such as dimethylamine; and the like. The amount of the reducing agent to be used varies depending on the type, and it is preferably 0.03 to 10 parts by weight for 1 part by weight of the peroxide. Among these initiators, a redox polymerization initiator combining a peroxide initiator and a reducing agent is more preferable. -1 0- ------: ί .. (Please read the notes on the back before filling in this page) ----- ^-The paper size of the book applies to the Chinese National Standard (CNS) Α4 specification (210 × 297) (Centi) 520379 A7 B7 5. Description of the invention () The emulsifier used in the polymerization is not particularly limited, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan Nonionic emulsifiers such as ethers; fatty acids and their salts of myristic acid, palmitic acid, oleic acid, and linoleic acid, higher alcohol sulfates, alkylsulfosuccinic acids, alkylbenzenesulfonates, aliphatic Anionic emulsifiers such as sulfonates; ammonium chlorides such as trimethylammonium chloride and dialkylammonium chloride; or cationic emulsifiers such as benzyl ammonium salt and quaternary salt; α, / 3- Copolymerizable emulsifiers such as sulfonic acid esters of unsaturated carboxylic acids, sulfate esters of α, 0-unsaturated carboxylic acids, and sulfoalkyl aromatic esters. It is particularly preferable to use an anionic emulsifier or a nonionic emulsifier. These emulsifiers may be used singly or in combination of two or more kinds, and the amount thereof is usually 0.1 to 9% by weight for the monomer mixture. In the polymerization, a polymerization auxiliary material such as a molecular weight adjuster, a particle size adjuster, an anti-aging agent, a chelating agent, and an oxygen trapping agent can be used as needed. The polymerization is usually carried out at a conversion of 90% or more, preferably 95% or more, and more preferably 99% or more. The particle size of the obtained latex is usually 0.07 to 0.3 // m, preferably 0.08 to 0.2 #m. If the particle size is too small, the viscosity of the latex is too high, it is difficult to handle, and the stability of the composition is reduced. On the other hand, when it is too high, the film-forming property of the dip-molded article is not good. The latex for impregnation molding of the present invention preferably contains a phenol-based compound having a free-radical chain prohibition as an anti-aging agent. The phenol-based compound is non-polluting to the impregnated molded article, has a low odor, and does not cause a problem of turning pink even when the impregnated molded article is chlorinated in a post process (excellent pinking resistance) ). In addition, the chlorination treatment is to solve the problem of dipping molding such as gloves. 1 1-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling in this page

、1T 經濟部智慧財產局員工消費合作社印製 520379 A7 B7 五、發明説明（） 物內部表面間密接，不易互相剝離問題的方法之一。 除苯酚系化合物外亦可使用芳香族胺化合物，對浸漬模 製物而言具污染性、且易引起臭味問題。此外，抗老化劑亦 可使用具過氧化物分解作用之化合物，惟會因熱、紫外線而 產生變黃色情形、且其單獨之抗老化效果小。 苯酚系化合物有單苯酚系化合物、雙、參、聚苯酚化合物 '硫代雙苯酚化合物等。其具體例係單苯酚化合物有2，6 -二·第3 -丁基苯酚、2，6 -二-第3 -丁基-4-甲基苯酣、2,4-二辛基苯酚、丁基羥基苯酚、2,6 -二-第3 -丁基-α -二甲基 胺基-對-甲酚、丁基化辛基化苯酚等；雙、參、聚苯酚化合 物有2,2’-亞甲基-雙- (6-α-甲基-苯甲基-對-甲酚）、 4,4’-次丁基雙（3-甲基-6-第3-丁基苯酚）、2,2’-亞甲基-雙- (4-甲基-6-第3-丁基苯酚）、對-甲酚與二環戊二烯之丁 基化反應生成物、1，3,5-三甲基-2,4,6-參（3,5-二-第3-丁基-4 -羥基苯甲基）苯、改性的聚烷基亞磷酸氯化多元苯酚 等，硫代雙苯酚化合物有4，4 ’ -硫代雙-(6 -第3 - 丁基-3 -甲 基苯酚）、4,4’-硫代雙- (6-第3-丁基-鄰-甲酚）等。 於苯酚系化合物中以在常溫下爲固體、且其熔點比製造浸 漬模製物時之最高溫度較低者較佳。通常，浸漬模製物之最 高溫度爲約1 20 °C。抗老化劑在常溫下爲液狀時會有臭味， 熔點較1 20 t爲高時、於浸漬模製時抗老化劑不會熔解、浸 漬模製物無法均勻地浸透。就考慮上述之點時，以使.用2，6 -二-第3 -丁基-4-甲基苯酚、對-甲酚與二環戊二烯之丁基化 -12- 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁) I 丁， * 、-'tv 經濟部智慧財產局員工消費合作社印製 520379 … —— — .A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（） 反應生成物等較佳。 抗老化劑之使用量視其目的之浸漬模製物要求的特性而 定，對100重量份浸漬固成分而言以0.1〜3重量份較佳、 更佳者爲0 · 3〜1重量份。若該使用量過少時，易引起熱 變性、紫外線變色性、強度降低之問題；而若過多時，會降 低耐熱變色性、耐光變色性、強度維持之添加效果。 於乳膠中添加抗老化劑之方法，沒有特別限制，就考慮 與乳膠之混合容易性時，通常以乳液或分散液之液狀分散 物添加。此等之分散物一般藉由乳液法或粉碎法予以調製。 乳液法係使視其所需藉由加熱成液狀之抗老化劑、乳化劑 及溫水充分高速攪拌而成乳液之方法。由於以水做爲介質， 可使用的抗老化劑之熔點通常爲水之沸點的1 00 °c以下、較 佳者爲9 0 t以下。 粉碎法係爲使無法使用乳液法之熔點高的固體予以機械 細粒化、且使其成分散物的方法。粉碎法使用葉輪式磨機、 噴射磨機等之乾式粉碎，與使用膠體磨機等之濕式粉碎法 。就藉由粉碎之到達粒徑小且粉碎時之發熱情形少而言以 濕式粉碎法較佳，其中，介質式濕式粉碎法較佳。介質式濕 式粉碎法係使用球磨機、高速珠磨機等，其中以藉由高速珠 磨機之粉碎較佳。 高速珠磨機法係在圓筒狀容器中塡充球狀介質，且使用 攪拌器旋轉軸予以高速回轉、在使介質運動中藉由將抗老化 劑供應給幫浦等予以分段式或連續式粉碎的方法。介質通常 -1 3 - (請先閱讀背面之注意事項再填寫本頁)， 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 520379 A7 B7 V. Description of the invention () One of the methods that the inner surfaces of objects are tightly connected and cannot be easily peeled from each other. An aromatic amine compound may be used in addition to the phenol-based compound, which is contaminating to the impregnated molded article and easily causes odor problems. In addition, anti-aging agents can also use compounds with peroxide decomposition, but they will turn yellow due to heat and ultraviolet rays, and their individual anti-aging effects are small. Phenol-based compounds include monophenol-based compounds, bis, ginseng, polyphenol compounds, and thiobisphenol compounds. Specific examples of the monophenol compound include 2,6-di · 3-3-butylphenol, 2,6-di-3-butyl-4-methylphenylhydrazone, 2,4-dioctylphenol, and butyl Hydroxyphenol, 2,6-di-third-butyl-α-dimethylamino-p-cresol, butylated octyl phenol, etc .; bis, ginseng, polyphenol compounds have 2,2 ' -Methylene-bis- (6-α-methyl-benzyl-p-cresol), 4,4'-methine bis (3-methyl-6-th-butylphenol), 2,2'-methylene-bis- (4-methyl-6-th-butylphenol), butylated reaction product of p-cresol and dicyclopentadiene, 1,3,5 -Trimethyl-2,4,6-ginseng (3,5-di-third-butyl-4-hydroxybenzyl) benzene, modified polyalkylphosphite chlorinated polyphenols, etc., thioxo The bisphenol compounds are 4,4'-thiobis- (6- 3rd-butyl-3 -methylphenol), 4,4'-thiobis- (6-th3-butyl-o-methyl) Phenol) and so on. Among the phenol-based compounds, those which are solid at ordinary temperature and have a lower melting point than the highest temperature at the time of manufacturing the impregnated molded product are preferred. Generally, the maximum temperature of the impregnated molding is about 120 ° C. When the anti-aging agent is liquid at normal temperature, it will have an odor. When the melting point is higher than 1 20 t, the anti-aging agent will not melt during the dipping molding, and the impregnated molded article cannot be uniformly impregnated. When considering the above points, use butylation of 2,6-di-third-butyl-4-methylphenol, p-cresol and dicyclopentadiene. 12- This paper applies China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before filling out this page) I Ding, *, -'tv Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 520379 —— ———— — .A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of invention () The reaction product is better. The amount of the anti-aging agent to be used depends on the characteristics required for the purpose of the impregnated molded article. For 100 parts by weight of the impregnated solid content, it is preferably 0.1 to 3 parts by weight, and more preferably 0.3 to 1 part by weight. If the amount is too small, problems such as thermal denaturation, ultraviolet discoloration, and reduction in strength are likely to be caused; and if it is excessive, the addition effects of heat discoloration resistance, light discoloration resistance, and strength maintenance may be reduced. The method of adding an anti-aging agent to latex is not particularly limited. When considering the ease of mixing with latex, it is usually added as a liquid dispersion of an emulsion or dispersion. These dispersions are generally prepared by an emulsion method or a pulverization method. The emulsion method is a method of making an emulsion by heating the liquid anti-aging agent, emulsifier and warm water at a high speed as needed. Since water is used as the medium, the melting point of the anti-aging agent that can be used is usually below 100 ° C, and more preferably below 90 t. The pulverization method is a method of mechanically granulating a solid having a high melting point, which cannot be used in the emulsion method, and dispersing it into a dispersion. The pulverization method uses a dry pulverization method such as an impeller mill, a jet mill, and a wet pulverization method using a colloid mill. The wet pulverization method is preferred in that the particle size reached by pulverization is small and the heat generation during pulverization is small, and the medium wet pulverization method is preferred. The medium-type wet pulverization method uses a ball mill, a high-speed bead mill, and the like. Among them, pulverization by a high-speed bead mill is preferred. The high-speed bead mill method is to fill a spherical medium in a cylindrical container, and use a stirrer rotating shaft to rotate at a high speed. In moving the medium, the anti-aging agent is supplied to the pump, etc. to be segmented or continuous. Method of crushing. Medium usually -1 3-(Please read the notes on the back before filling this page)

訂Order

本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 520379 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（） 係使用直徑爲〇 . 5mm以上、較佳者爲0 · 5〜1 Omm、更佳者爲 0 . 5〜3 m πι之小粒徑珠。珠之密度通常爲2 g / c m3以上。珠 之材質係使用锆等之高硬度陶瓷、鋼等之高硬度金屬。珠之 較佳塡充量就考慮粉碎效率而言以60〜9 5%較佳、更佳者爲 70 〜85% 。 本發明之浸漬模製物係使上述浸漬模製用乳膠藉由常法 予以浸漬模製而得者。通常，浸漬模製係使模具浸漬於浸漬 模製用配合液中，且使乳膠沉澱於模具表面後，使模具自 浸漬模製用配合液拉出、乾燥與予以進行。浸漬模製法之具 體例如直接浸漬法、陽極凝固浸漬法、悌古凝固浸漬法等。 浸漬模製用配合液中除浸漬模製用乳膠外，通常可配合 加硫劑（交聯劑）、爲使乳膠金屬離子交聯之加硫助劑、加硫 促進劑、做爲pH値調整劑之鹼等。而且視其所需可配合抗 老化劑、塡充劑、增黏劑等。本發明之浸漬模製用乳膠可單 獨或二種以上組合使用，在不損及本發明目的之範圍內亦 可倂用其他的乳膠。 於本發明中可使用做爲交聯劑之硫或硫化合物。其使用量 對100重量份乳膠固成分而言通常爲0.3〜5重量份、較佳 者爲0.5〜3重量份。此外，爲更爲提高機械強度時，以加 入氧化鋅 '氧化鎂、氧化鉛等之金屬氧化物較佳、更佳者爲 氧化鋅。其使用量對100重量份乳膠固成分而言通常爲0>1 〜5重量份、較佳者爲0.5〜3重量份。若該使用量過少時 強度變小，反之，若過多時由於影響強度等之添加效果飽 -14- 本^用中賴家標準（CNS )峨格（21GX297公襲） (請先閲讀背面之注意事項再填寫本頁)This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 520379 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () Use a diameter of 0.5mm or more, preferably 0 5 ~ 1 Omm, more preferably 0.5 ~ 3 m π small particle diameter beads. The density of the beads is usually above 2 g / c m3. The material of the beads is a high-hardness ceramic such as zirconium or a high-hardness metal such as steel. In terms of pulverization efficiency, the preferred amount of beads is preferably 60-95%, and more preferably 70-85%. The dip-molded article of the present invention is obtained by dip-molding the above-mentioned latex for dip-molding by a conventional method. Generally, the immersion molding is performed by immersing a mold in a compounding solution for immersion molding, and precipitating the latex on the surface of the mold, and then pulling out the mold from the compounding solution for immersion molding, drying, and performing. Specific examples of the immersion molding method include a direct immersion method, an anodic coagulation immersion method, and an ancient coagulation immersion method. Except for the latex for impregnation molding, the compounding solution for impregnation molding can usually be compounded with a vulcanization agent (crosslinking agent), a vulcanization aid for crosslinking the latex metal ions, a vulcanization accelerator, and pH adjustment. Agent base. In addition, anti-aging agents, fillers, and thickeners can be added as required. The latex for dipping molding of the present invention may be used alone or in combination of two or more kinds, and other latexes may be used as long as the purpose of the present invention is not impaired. Sulfur or sulfur compounds which can be used as a cross-linking agent in the present invention. The amount used is usually 0.3 to 5 parts by weight, preferably 0.5 to 3 parts by weight for 100 parts by weight of the latex solid content. In addition, in order to further improve the mechanical strength, zinc oxide is preferably added to metal oxides such as zinc oxide, magnesium oxide, and lead oxide. The amount used is usually 0 to 1 part by weight, and preferably 0.5 to 3 parts by weight, for 100 parts by weight of the latex solid content. If the amount is too small, the strength will be small. On the contrary, if the amount is too large, it will be full due to the addition effect that affects the strength. (Fill in this page again)

520379 A7 B7 五、發明説明（） 和、故不經濟。亦可僅以此等之金屬氧化物交聯，惟僅以金 屬交聯時容易使質感變硬，故以倂用硫與金屬氧化物以使 硫交聯與金屬交聯共存較佳。 於浸漬模製中使模具於浸漬配合液之前拉出或使模具自 配合液中拉出後，必須以凝固劑處理。處理方法係有使浸漬 前之模具浸漬於凝固劑之溶液中以附著於模具的方法，於 沉澱有乳膠之模具中使凝固劑之溶液振動的方法等。凝固劑 例如有硝酸鈣、氯化鈣等之多價金屬鹽。 自浸漬模製用配合液中拉出後，進行溫水處理或熱處理 。藉由進行溫水處理或熱處理，除去多餘的單體及配合助 劑、且促進共聚物之交聯反應。溫水處理或熱處理之方法沒 有特別的限制，例如使沉澱有乳膠之模具浸漬於溫水中的 方法、於烤箱等之中在沉澱有乳膠之模具上吹予溫風的方法 、在沉澱有乳膠之模具中照射紅外線的方法等。 本發明係以如此製得浸漬模製物。模製物之形狀沒有特別 的限制，具體例如橡皮手套、薄物手套、中厚手套、支援手 套、奶嘴、帶橡皮囊吸液體玻璃管、水枕、導尿管、氣球、 娃娃等。其中，以本發明之浸漬模製用乳膠之厚度爲〇 . 1〜 〇 . 3mm之薄物手套用極爲有用，使用該乳膠予以模製之薄 物手套，由於不會引起蛋白過敏、且質感柔軟、機械強度優 異，故可適合於手術用及診斷用。另外，浸漬模製物視其所 需使其表面塗覆滑石、碳酸鈣等之無機粒子；澱粉粒子、聚 苯乙烯粒子等之有機粒子；矽油等。 -1 5 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210'乂297公釐） (請先閲讀背面之注意事項再填寫本頁)520379 A7 B7 V. Description of the invention It is also possible to crosslink only these metal oxides, but it is easy to harden the texture when only metal crosslinks are used. Therefore, it is better to use sulfur and metal oxides to coexist sulfur crosslinks and metal crosslinks. In the dipping molding, the mold must be pulled out before the dipping solution is immersed or the mold must be pulled out from the compounding liquid, and must be treated with a coagulant. Treatment methods include a method of immersing a mold before immersion in a solution of a coagulant to adhere to the mold, and a method of vibrating a solution of the coagulant in a mold in which latex is deposited. Examples of the coagulant include polyvalent metal salts such as calcium nitrate and calcium chloride. After being pulled out from the compounding solution for immersion molding, warm water treatment or heat treatment is performed. By performing warm water treatment or heat treatment, excess monomers and auxiliary agents are removed, and the crosslinking reaction of the copolymer is promoted. The method of warm water treatment or heat treatment is not particularly limited, such as a method of immersing a mold in which latex is deposited in warm water, a method of blowing warm air on a mold in which latex is deposited in an oven, or the like, A method of irradiating infrared rays in a mold. In the present invention, an impregnated molded article is thus obtained. The shape of the molded article is not particularly limited, and specific examples include rubber gloves, thin object gloves, medium-thick gloves, support gloves, pacifiers, glass tubes with rubber pouches, water pillows, urinary catheters, balloons, dolls, and the like. Among them, the thin object gloves with the thickness of 0.1 to 0.3 mm of the latex for dip molding of the present invention are extremely useful. The thin object gloves molded by using the latex do not cause protein allergy, and the texture is soft and mechanical. Excellent strength, so it is suitable for surgery and diagnostics. In addition, the surface of the impregnated molding is coated with inorganic particles such as talc, calcium carbonate, etc .; organic particles such as starch particles, polystyrene particles, etc .; -1 5-This paper size is applicable to Chinese National Standard (CNS) A4 (210 '乂 297mm) (Please read the precautions on the back before filling this page)

1訂 經濟部智慧財產局員工消費合作社印製 520379 A7 _ B7 五、發明説明（） 【實施例】 於下述中以實施例更詳細地說明本發明，惟本發明不受此 等所限制。而且，沒有特別限制時，實施例及比較例中之份 及％皆以重量爲基準，乳膠之重量係以固成分換算。此外， 實施例中各種測定値係藉由下述之方法製得。 (1 g共聚物乳膠之總酸基量） 在1 50ml乙蒸餾水洗淨的玻璃容器中加入50g固成分濃度 調整爲2重量％之共聚物乳膠，固定於溶液導電率計（京都 電子工業公司：CM - 1 1 7、使用晶胞型：K - 1 2 1 )予以攪拌。 然後，持續攪拌至鹽酸添加終了。爲使共聚物乳膠之導電率 爲2.5〜3.0(mS)，在共聚物乳膠中添加0.1規定的氫氧化 鈉（合光純藥公司製：試藥特級）後，經過6分鐘後測定導電 度。以該値做爲測定開始時之導電度。在該共聚物乳膠中添 加0 . 5 m 1之0 . 1規定的鹽酸（和光純藥公司製：試藥特級）， 於3 0秒後測定導電度。再添加0 . 5 m 1之0 . 1規定的鹽酸，於 3 0秒後測定導電度。以3 0秒之間隔重複該操作直至共聚物 乳膠之導電度在測定開始時之導電度以上。 使所得導電度數據以縱軸：導電度（mS )、橫軸：所添加鹽 酸之累計量（微莫耳）之圖表上標示時，可得如第1圖之具3 個彎曲點之鹽酸量-導電度曲線。使3個彎曲點之X座標及 鹽酸添加終了時的X座標爲數値由小至大之順序各爲P 1、 P2、P3及P4，以X座標爲零至PI、P1至P2、P2至P3及 P3至P4之4區份內的數據各藉由最小二乘法求取近似直線 -1 6 - 本紙張尺度適用中國國家標準（CNS )八4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)Order 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 520379 A7 _ B7 V. Description of the Invention () [Examples] The following describes the present invention in more detail with examples, but the present invention is not limited by these. In addition, when there is no particular limitation, the parts and% in the examples and comparative examples are based on weight, and the weight of the latex is converted into solid content. In addition, various measurements in the examples were prepared by the following methods. (Total acid group content of 1 g copolymer latex) 50 g of copolymer latex whose solid content concentration was adjusted to 2% by weight was added to a glass container washed with 150 ml of distilled water, and fixed to a solution conductivity meter (Kyoto Electronics Industry Corporation: CM-1 1 7. Use unit cell type: K-1 2 1) and stir. Then, continue stirring until the end of the hydrochloric acid addition. In order to make the copolymer latex have an electrical conductivity of 2.5 to 3.0 (mS), 0.1% of sodium hydroxide (manufactured by Heguang Pure Pharmaceutical Co., Ltd .: test grade) was added to the copolymer latex, and the conductivity was measured after 6 minutes. The conductivity was measured at the beginning of this measurement. To this copolymer latex was added 0.5 m 1 of 0.1 hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd .: Test Grade), and the conductivity was measured after 30 seconds. Then add 0.5 m 1 of 0.1 hydrochloric acid, and measure the conductivity after 30 seconds. This operation was repeated at 30 second intervals until the conductivity of the copolymer latex was more than that at the start of the measurement. When the obtained conductivity data is marked on the graph of vertical axis: conductivity (mS), horizontal axis: cumulative amount of added hydrochloric acid (micromolar), the amount of hydrochloric acid with three bending points can be obtained as shown in FIG. 1 -Conductivity curve. Let the X coordinate of the three bending points and the X coordinate at the end of the addition of hydrochloric acid be numbers. The order from small to large is P 1, P2, P3, and P4, and the X coordinate is zero to PI, P1 to P2, and P2 to The data in the 4 areas of P3 and P3 to P4 are each obtained by the least squares method to approximate the straight line-1 6-This paper size applies to China National Standard (CNS) 8 4 specifications (210X297 mm) (Please read the back (Please fill in this page again)

訂 經濟部智慧財產局員工消費合作社印製 A7 520379 B7 五、發明説明（） LI、L2、L3及L4。L1與L2之交點的X座標爲A1(微莫耳） 、L2與L3之交點的X座標爲A2(微莫耳）、L3與L4之交點 的X座標爲A3(微莫耳）。 lg共聚物之表面酸基量及lg共聚物之水相酸基量係各由 式（a )及式（b )以鹽酸換算的微當量供應。因此，1 g共聚物 乳膠之酸基量以式（c)表示時係爲此等式（a)及式（b)之合計 〇 (a) lg聚合物之表面酸基星zAZ-Al (b) lg聚合物之水相中酸基量= A3-A2 (c ) 1 g聚合物乳膠之總酸基量=(a ) + ( b ) (質感） 使浸漬模製物以啞鈴變形2號穿孔以製作試驗片，以拉 伸速度5 00mm/分拉伸、測定拉伸率爲3 00%時之拉伸強度。 數値愈小者質感愈柔軟。 (拉伸強度） 使上述之試驗片以拉伸速度爲500mm/分拉伸，測定斷裂 前之拉伸強度。 (水浸漬後強度） 使上述之試驗片浸漬於水中3小時，且擦拭多餘的水分 後，以拉伸速度爲500mm/分拉伸，測定直至斷裂之拉伸速 度。 (CS 値） 在100ml之燒杯中各加入30ml之0 . 1%濃度不同的NaCl溶 -1 7 - 本紙張尺度適用巾關家標準（CNS ) A4規格（210X297公襲) " (請先閱讀背面之注意事項再填寫本頁) ------訂--.---- 經濟部智慧財產局員工消費合作社印製 520379 A7 B7 五、發明説明（） 液，於其中滴入1滴（約〇 · 2 cm3 )乳膠，且測定乳膠凝固時 之濃度。使其各爲乳膠固成分濃度5%、45%，此時之測定値 各爲CS1値、CS2値。固成分濃度爲5%之乳膠係在固成分濃 度4 5%之乳膠中加入軟水予以調製。 (成膜性） 使形成於手套型表面之固體皮膜物，以目視觀察自其剝 落所得的浸漬模製物之成膜狀態，以下述之基準評估。 評估標準〇：形成全部沒有斑點之連續膜 △:形成部份有斑點之連續膜 X :形成有龜裂、穴等之不連續膜 (膜厚及其單分散性比） 測定20個拉出有浸漬模製物之線部分的膜厚，求取其平 均値級標準偏差。膜厚以平均値表示，且膜厚之單分散性比 係以平均値除以標準偏差、以百分率表示。數値愈小者可得 均勻的成膜性。 (耐油性） 使浸漬模製物穿孔成直徑20mm之圓形試驗片，在25 °C下 浸漬於所定的試驗油中4 8小時後，測定試驗片之面積、求 取使試驗由中浸漬前與浸漬後之面積變化除以浸漬前之面 積之値（面積膨脹率），做爲耐油性之指標。數値愈小者耐油 性愈高。 (耐熱變色性） -18- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 520379 B7 V. Description of Invention () LI, L2, L3 and L4. The X coordinate of the intersection of L1 and L2 is A1 (micromolar), the X coordinate of the intersection of L2 and L3 is A2 (micromolar), and the X coordinate of the intersection of L3 and L4 is A3 (micromolar). The amount of the surface acid groups of the lg copolymer and the amount of the acid phase of the water phase of the lg copolymer are each supplied by the microequivalent equivalent of formula (a) and formula (b) in terms of hydrochloric acid. Therefore, when the acid group content of 1 g of copolymer latex is expressed by formula (c), it is the total of the equations (a) and (b). (A) The surface acid group of the lg polymer zAZ-Al (b ) The amount of acid groups in the aqueous phase of lg polymer = A3-A2 (c) The total amount of acid groups in 1 g of polymer latex = (a) + (b) (texture) Deformation of the impregnated molding with dumbbells No. 2 perforation A test piece was produced, and the tensile strength was measured at a tensile speed of 500 mm / min and a tensile strength of 300% was measured. The smaller the number, the softer the texture. (Tensile strength) The above test piece was stretched at a tensile speed of 500 mm / min, and the tensile strength before breaking was measured. (Strength after water immersion) The test piece described above was immersed in water for 3 hours, and after excess water was wiped, the test piece was stretched at a tensile speed of 500 mm / min, and the tensile speed until fracture was measured. (CS 値) In a 100ml beaker, add 30ml of 0.1% NaCl with different concentration to each other. 1-This paper size applies to the family standard (CNS) A4 size (210X297 public attack) " (Please read first Note on the back, please fill out this page) ------ Order --.---- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 520379 A7 B7 V. Description of the invention () Liquid, drip 1 drop into it (About 0.2 cm3) latex, and the concentration at which the latex coagulated was measured. It was made into the latex solid content concentration of 5% and 45% respectively, and the measurement at this time was CS1CS and CS2 値 respectively. The latex with a solid content of 5% is added to the latex with a solid content of 4 5% by adding soft water to prepare it. (Film-forming property) The film-formation state of the solid film material formed on the glove-type surface was visually observed from the peeling of the impregnated molded article, and evaluated based on the following criteria. Evaluation Criteria 〇: Formation of all continuous films without spots △: Formation of partially continuous films with spots X: Formation of discontinuous films with cracks, pits, etc. (film thickness and monodispersity ratio) 20 pull-outs were measured The film thickness of the line portion of the dip-molded article was determined as the average standard deviation of the grade. The film thickness is expressed as an average 値, and the monodispersity ratio of the film thickness is expressed as a percentage divided by the average 値 divided by the standard deviation. The smaller the number is, the more uniform the film-forming property is. (Oil resistance) A circular test piece having a diameter of 20 mm was perforated by the impregnated molded article, and immersed in a predetermined test oil at 25 ° C for 48 hours. Then, the area of the test piece was measured, and the test was performed before the impregnation of the test medium. Divide the area change after immersion by the area before immersion (area expansion rate) as an index of oil resistance. The smaller the number, the higher the oil resistance. (Heat-resistant discoloration) -18- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

、1T 經濟部智慧財產局員工消費合作社印製 520379 A7 B7 五、發明説明（） 將浸漬模製物之試驗片置於烤箱中，在大氣氣氛中、 1 6 0 °C下加熱1 0分鐘後，以色差計（史卡（譯音）試驗機股份 有限公司）來測定黃色指數（黃色度：以下稱爲「γ . K」）。 數値愈小者耐熱變色性愈優異。 (耐光變色性） 使浸漬模製物之試驗片使用耐光試驗機（史卡（譯音）試 驗機股份有限公司：長效型），在大氣氣氛中、63 °C下紫外 線照射1 6小時後，以色差計測定Y · I ·。數値愈小者耐光變 色性愈優異。 (耐變粉紅色性） 在混合有9 9份5%次氯酸鈉水溶液與1份濃鹽酸所調整的 游離氯溶液中，使浸漬模製物浸漬48小時，取出後以2%銨 水溶液充分洗淨，另予以水洗後於5 0 °C之轉鼓機乾燥。以 色差計測定該浸漬模製物之a*値（紅色度）。數値愈小者耐 變粉紅色性愈優異。 (實施例1 ) 在經氮氣取代的聚合反應器中加入3 4份丙烯睛、5 9份 1,3 -丁二烯、7份甲基丙烯酸、0.5份分子量調整劑（TDM : 第3 -十二基硫醇）、1 50份軟水、2 · 5份乳化劑（十二苯磺酸 鈉）、0 · 2份啓始劑（過硫酸鉀）及0 · 1份還原劑（乙二胺四醋 酸），使聚合溫度保持於3 0 °C、使其反應2 0小時後，添加 反應停止劑以使聚合終了。 自所得的乳膠中除去未反應單體後，調整共聚物乳膠之 -19- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China 520379 A7 B7 V. Description of the invention () Put the test piece of the impregnated molding in the oven, and heat it at 160 ° C for 10 minutes in the atmosphere The yellowness index (yellowness: hereinafter referred to as "γ.K") was measured with a color difference meter (Shika (Transliteration) Testing Machine Co., Ltd.). The smaller the number, the better the heat discoloration resistance. (Lightfastness) After using a lightfastness tester (Shika Tester Co., Ltd .: long-lasting type) for the test piece of the impregnated molded article, the ultraviolet light was irradiated at 63 ° C for 16 hours in the atmosphere. Measure Y · I · with a colorimeter. The smaller the number, the better the light discoloration resistance. (Pink resistance) In a free chlorine solution prepared by mixing 99 parts of a 5% sodium hypochlorite aqueous solution and 1 part of concentrated hydrochloric acid, immerse the impregnated molding for 48 hours, and take it out and wash it thoroughly with a 2% ammonium aqueous solution. It was washed with water and dried on a drum machine at 50 ° C. The a * 値 (redness) of the impregnated molding was measured by a color difference meter. The smaller the number, the better the pinking resistance. (Example 1) In a polymerization reactor substituted with nitrogen, 34 parts of acrylonitrile, 59 parts of 1,3-butadiene, 7 parts of methacrylic acid, and 0.5 parts of molecular weight modifier (TDM: 3rd to 10th) were charged. Diyl mercaptan), 150 parts of soft water, 2.5 parts of emulsifier (sodium dodecylsulfonate), 0.2 parts of starter (potassium persulfate), and 0.1 parts of reducing agent (ethylenediamine tetra Acetic acid), the polymerization temperature was maintained at 30 ° C, and the reaction was allowed to proceed for 20 hours, and then a reaction stopper was added to complete the polymerization. After removing the unreacted monomer from the obtained latex, adjust the copolymer latex. -19- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

經濟部智慧財產局員工消費合作社印製 520379 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（） pH値及濃度，製得固成分濃度45%、pH値爲8.3之共聚物 乳膠A。所得乳膠之物性如表1所示。 使7份混合有1 . 〇份硫、1 . 〇份氧化鋅、1 · 0份氧化鈦及 〇 . 〇 3份氫氧化鉀、3 . 2份水所調製的固成分濃度5 0%之加硫 劑分散溶液中混合於2 2 0份固成分濃度4 5 %之乳膠A中，以 製得浸漬模製用配合液。另外，將手套型浸漬於混合2 0份 硝酸銀、0 · 0 5份非離子性乳化劑（耶麻魯肯8 1 0 :花王公司 製品）及80份水所調製的固成分濃度爲20%之凝固劑溶液1 小時後，拉出後在5 0 °C下乾燥3分鐘，使凝固劑附著於手 套型上。然後，使附著有凝固劑之手套型浸漬於浸漬模製用 配合液中6分鐘，拉出後使該手套型在20 °C下乾燥3分鐘 。再使該手套型在80 °C下乾燥機中乾燥20分鐘，再昇溫至 12CTC，且熱處理25分鐘、在手套型表面上製得固體皮膜物 。最後，使該固體皮膜物自手套型剝離且製得手套形狀之 浸漬模製物。該浸漬模製物之評估結果如表1所示。 (實施例2〜4、比較例1〜3 ) 除改變單體組成外，與實施例1相同製得固成分濃度4 5 %、p Η 8 . 3之共聚物乳膠B〜G。所得乳膠之物性如表1 所示。 除各使用乳膠Β〜G來取代乳膠Α外，與實施例1相同製 得浸漬模製物。此等浸漬模製物之評估結果如表1所示。 由表1之浸漬模製物的評估結果可知，使用本發明之共聚 物乳膠的實施例1〜4之浸漬模製物，質感柔軟、拉伸強度 -20- 本紙張尺度適用中國國家標準（cns ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 520379 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () pH 値 and concentration, a copolymer latex with a solid content concentration of 45% and a pH 8.3 of 8.3 A. The physical properties of the obtained latex are shown in Table 1. 7 parts were mixed with 1.0 part of sulfur, 1.0 part of zinc oxide, 1.0 part of titanium oxide, 0.03 part of potassium hydroxide, and 3.2 parts of water to add a solid content concentration of 50%. The sulfur agent dispersion solution was mixed with 220 parts of latex A having a solid content concentration of 45% to obtain a compound solution for impregnation molding. In addition, a glove type was immersed in a mixture of 20 parts of silver nitrate, 0.5 parts of non-ionic emulsifier (Yamaluken 8 1 0: Kao Corporation), and 80 parts of water. After 1 hour, the agent solution was pulled out and dried at 50 ° C for 3 minutes to allow the coagulant to adhere to the glove type. Then, the glove type to which the coagulant was adhered was immersed in the compounding solution for dipping molding for 6 minutes, and the glove type was dried at 20 ° C for 3 minutes after being pulled out. The glove was dried in a dryer at 80 ° C for 20 minutes, and then heated to 12 CTC, and heat-treated for 25 minutes to prepare a solid film on the surface of the glove. Finally, the solid film was peeled from the glove type and a glove-shaped impregnated molded article was obtained. The evaluation results of the impregnated molding are shown in Table 1. (Examples 2 to 4, Comparative Examples 1 to 3) Except that the monomer composition was changed, copolymer emulsions B to G having a solid content concentration of 45% and pΗ8.3 were prepared in the same manner as in Example 1. The physical properties of the obtained latex are shown in Table 1. Except that each of latexes B to G was used in place of latex A, an impregnated molded article was obtained in the same manner as in Example 1. The evaluation results of these impregnated moldings are shown in Table 1. From the evaluation results of the impregnated moldings in Table 1, it can be known that the impregnated moldings of Examples 1 to 4 using the copolymer latex of the present invention have soft texture and tensile strength of -20. This paper size applies Chinese national standards (cns ) A4 size (210X297mm) (Please read the notes on the back before filling this page)

520379 Α7 Β7 五、發明説明（） 及水浸漬後強度高。對此而言，使用總酸基量小的乳膠E時 ’質感雖柔軟、惟其拉伸強度及水浸漬後之強度低（比較例 1 )。而且’總酸基量大的乳膠F或乳膠G時，拉伸強度雖 高、惟質感硬且於水浸漬後之強度變低（比較例2、比較例 3 ) ° (實施例5〜1 〇 ) 除使用表2所示之單體混合物外，與實施例1相同地製 得乳膠Η〜Μ。惟乳膠Μ於調製後乳膠之p Η値爲5 · 6。 乳膠Η〜Μ之總酸基量係對1 g共聚物而言在0 · 1 5 〜1 .8毫當量之範圍內。測定乳膠Η〜Μ之CS 1値及C S 2値，結果如表2所示。 除使用使7份混合有1 · 0份硫、1 . 5份氧化鋅、0 · 7份 氧化鈦及0 . 0 3份氫氧化鉀、3 . 2份水所調製的固成分濃度 5 0%之加硫劑，且使用乳膠Η〜Μ來取代乳膠Α外，與實施 例1相同製得模製物。此等浸漬模製物之評估結果如表2所 不 ° 實施例5〜1 〇之浸漬模製物之質感柔軟且拉伸強度高， 在例示之範圍內其耐油性沒有很大的差別。而且，水浸漬後 之強度亦高。 由表2之結果可知，使用CS1値及CS2値爲1 . 5%〜3 . 0% 之乳膠Η〜J所得的實施例5〜7之浸漬模製物，具有優異 的均勻成膜性。使用CS2値小於1 . 5%之乳膠Κ及Μ時，成膜 性不充分且必須比製作沒有斑點之膜使用較爲多量的乳膠（ -21 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁)520379 Α7 Β7 5. Description of the invention () and high strength after water immersion. In this regard, when using latex E having a small total acid group, the texture is soft, but its tensile strength and strength after water immersion are low (Comparative Example 1). Moreover, in the case of latex F or latex G having a large total acid group, although the tensile strength is high, the texture is hard and the strength after water immersion becomes low (Comparative Example 2, Comparative Example 3) ° (Examples 5 to 1). ) Latex Η ~ M was obtained in the same manner as in Example 1 except that the monomer mixture shown in Table 2 was used. However, the p Η 値 of latex M after preparation is 5.6. The total acid group content of the latex Η ~ M is in the range of 0.15 to 1.8 milliequivalents for 1 g of the copolymer. The CS 1CS and C S 2 値 of latex Η to Μ were measured. The results are shown in Table 2. In addition to using 7 parts mixed with 1.0 part of sulfur, 1.5 parts of zinc oxide, 0.7 parts of titanium oxide and 0.3 part of potassium hydroxide, 3.2 parts of water to prepare a solid content concentration of 50% A vulcanizing agent was used, and latex A ~ M was used instead of latex A, and a molded article was prepared in the same manner as in Example 1. The evaluation results of these impregnated moldings are as shown in Table 2. The impregnated moldings of Examples 5 to 10 are soft in texture and high in tensile strength, and there is no great difference in oil resistance within the range exemplified. In addition, the strength after water immersion is high. From the results in Table 2, it is understood that the impregnated molded articles of Examples 5 to 7 obtained by using CS1 値 and CS2 値 at 1.5% to 3.0% of latex Η ~ J have excellent uniform film-forming properties. When using CS2 値 latex K and M of less than 1.5%, the film-forming property is insufficient and a larger amount of latex must be used than the film without spots (-21-This paper size applies to China National Standard (CNS) Α4 specifications (210 X 297 mm) (Please read the notes on the back before filling this page)

經濟部智慧財產局員工消費合作社印製 520379 A7 B7 五、發明説明（） 實施例8、實施例1 〇 )。而若使用CS 1値大於3 . 0%之乳膠L 時，成膜性稍微不充分、且必須比製作沒有斑點之膜使用較 爲多量的乳膠（實施例9 )。 (實施例1 1〜1 6 ) 除使用表3所示之單體混合物外，與實施例1相同地製得 乳膠N〜T，對1 00份各乳膠之固成分而言添加0 . 5份抗老 化劑。除使用含有此等抗老化劑之乳膠外，予實施例1相同 地製得浸漬模製物。 而且，藉由珠磨機之分散方法係採用設有幾魯克尼亞（ 譯音）製之直徑0 · 5mm之珠（裝入量：混練容量之80%)之連接 混練分散機（RG-100 :荒木鐵工製（股）），藉由乳液法之分 散方法係採用在5 5 °C之條件下使用TK均混機（4D型：特殊 機化工業製），各調製固成分濃度50%之分散液。 此等之浸漬模製物的評估結果如表3所示。而且，皆具有 均勻成膜性、質感柔軟、拉伸強度及水浸漬後之強度高。 由表3可知，添加苯酚系化合物時，所得的浸漬模製物 具有優異的耐熱變色性及耐光變色性及耐變粉紅色性（實施 例1 1〜1 3 )。對此而言，添加芳香族胺化合物時，耐熱變色 性及耐光變色性雖佳，惟耐變粉紅色性稍不佳（實施例1 4 及1 5 )。此外，添加具過氧化物分解作用之二硫胺基甲酸鹽 時，與苯酚系化合物相比其耐熱變色性、耐光變色性、耐變 粉紅色性皆不佳（實施例1 6 )。 【發明效果】 -22- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 520379 A7 B7 V. Description of the Invention () Example 8, Example 10). When using a latex L having a CS 1 値 greater than 3.0%, the film-forming property is slightly insufficient, and a larger amount of latex must be used than in making a film without spots (Example 9). (Example 1 1 ~ 1 6) Except using the monomer mixture shown in Table 3, latex N ~ T was prepared in the same manner as in Example 1, and 0.5 part was added to 100 parts of the solid content of each latex. Anti-aging agent. An impregnated molded article was prepared in the same manner as in Example 1 except that a latex containing these anti-aging agents was used. Furthermore, the dispersing method by the bead mill is a connected kneading and dispersing machine (RG-100) equipped with beads of a diameter of 0.5 mm (loading amount: 80% of the kneading capacity) made of several Rukhonia (transliteration). : Araki Iron Works Co., Ltd., the dispersion method by the emulsion method uses a TK homomixer (4D type: made by special mechanized industry) at 5 5 ° C, each with a solid content concentration of 50% Its dispersion. The evaluation results of these impregnated moldings are shown in Table 3. In addition, they all have uniform film-forming properties, soft texture, high tensile strength, and high strength after water immersion. As can be seen from Table 3, when the phenol-based compound is added, the obtained impregnated molded article has excellent heat discoloration resistance, light discoloration resistance, and pinking resistance (Examples 1 to 1 3). On the other hand, when an aromatic amine compound is added, although heat discoloration resistance and light discoloration resistance are good, pinking resistance is slightly inferior (Examples 1 4 and 15). In addition, when a dithiocarbamate having a peroxide decomposition effect was added, the heat discoloration resistance, light discoloration resistance, and pinking resistance were inferior to those of a phenol-based compound (Example 16). [Effects of the invention] -22- This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

訂 經濟部智慧財產局員工消費合作社印製 520379Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 520379

五、發明説明（） 、 用 軟製 柔模 感漬 質浸 、 之 敏物 過該 白得 蛋製 起爲 弓及 會以 不物 得製 製模 可漬 明浸 發的 本異 由優 藉度 Jru 〈nf 比強。 如械膠 機乳 水 之 膠 乳 物 聚 共 及 量 基 酸 面 表 之 物 聚 ] 共 明 以 說 示 單 表 簡 1 係 之圖圖 面 1—I 1—I 圖第第 乳 物 聚 共 時. 酸 鹽 加 添 中 膠 乳 物 聚 共 於 法 。 方化 定變 測的 的度 量電 基導 酸之 相膠 (請先閱讀背面之注意事項再填寫本頁) ·_· T-訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210'乂297公釐） 520379 A7 B7 五、發明説明（） 經濟部智慧財產局員工消費合作社印製 表1 實施例 比較例 1 2 3 4 1 2 3 (單體） 丙烯腈(份） 34 45 20 25 苯乙烯(份） 20 50 50 1，3-丁二烯 (份） 59 65 50 48 50 50 60 甲基丙烯酸 (份） 7 15 30 5 丙烯酸(份） 5 10 乳膠 A B C D E F G (乳膠物性） 總酸基量 (微當量） 1.07 1.51 1.02 0.46 0.02 3.25 2.44 (浸漬模製 物之物性） 質感 (kg/cm2) 46 38 52 30 10 100 82 拉伸強度 (kg/cm2) 360 310 370 250 60 540 480 水浸漬後強 度(kg/cm2) 250 200 260 240 51 90 120 -24 - (請先閲讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 520379 A7 B7 五、發明説明（） 經濟部智慧財產局員工消費合作社印製 表2 實施例 5 6 7 8 9 10 (單體） 丙烯腈(份） 35 45 35 40 20 30 1,3-丁二烯 (份） 50 50 63 57 70 60 甲基丙烯酸 (份） 15 5 2 3 10 10 乳膠 Η I J Κ L Μ (乳膠物性） CS1 値(％) 2.7 2.3 2.2 1.4 3.3 1.9 CS2 値(％) 2.2 1.7 1.5 0.6 2.5 1.2 (浸漬模製物 之物性） 成膜性 〇 〇 〇 X Δ X 膜厚(mm) 0.2 0.26 0.29 0.45 0.18 0.32 膜厚單分散 性比(％) 6 4.5 3.8 2.8 12.2 3.5 質感(kg/cm2) 60 44 38 40 54 57 拉伸強度 (kg/cm2) 420 340 300 310 390 400 耐油性 (%)JIS #3 2 0 2 2 3 2 烏賊油 11 4 12 12 12 11 汽油 23 12 22 21 26 23 -25- (請先閱讀背面之注意事項再填寫本頁)V. Description of the invention (), Use soft-made soft mold to soak the texture, soak the sensitive material over the white egg to make a bow, and use the unavailable mold to stain the hair. Jru <nf is stronger. For example, the polymer of the latex of the mechanical rubber emulsion and the amount of the acid-based surface of the polymer] are shown to show a single table and a series of drawings 1-I 1-I Addition of acid latex to latex copolymerization method. The adhesive of measuring electric conductivity based on Fanghua's variable measurement (please read the notes on the back before filling this page) Standard (CNS) A4 specification (210 '乂 297 mm) 520379 A7 B7 V. Description of the invention () Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 1 Example Comparative Example 1 2 3 4 1 2 3 (single) Acrylonitrile (parts) 34 45 20 25 Styrene (parts) 20 50 50 1,3-butadiene (parts) 59 65 50 48 50 50 60 Methacrylic acid (parts) 7 15 30 5 Acrylic acid (parts) 5 10 Latex ABCDEFG (latex physical properties) Total acid groups (micro equivalents) 1.07 1.51 1.02 0.46 0.02 3.25 2.44 (physical properties of impregnated molding) Texture (kg / cm2) 46 38 52 30 10 100 82 Tensile strength (kg / cm2) 360 310 370 250 60 540 480 Strength after water immersion (kg / cm2) 250 200 260 240 51 90 90 120 -24-(Please read the precautions on the back before filling out this page) The paper size for this edition applies Chinese National Standard (CNS) A4 size (210 X 297 mm) 520379 A7 B7 V. Description of the invention () Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Table 2 Example 5 6 7 8 9 10 (monomer) Acrylonitrile (parts) 35 45 35 40 20 30 1,3-butadiene ( Parts) 50 50 63 57 70 60 Methacrylic acid (parts) 15 5 2 3 10 10 Latex Η IJ Κ L Μ (latex physical properties) CS1 値 (%) 2.7 2.3 2.2 1.4 3.3 1.9 CS2 値 (%) 2.2 1.7 1.5 0.6 2.5 1.2 (Physical properties of the impregnated molded product) Film-forming property 0.0000 Δ X Film thickness (mm) 0.2 0.26 0.29 0.45 0.18 0.32 Film thickness monodispersity ratio (%) 6 4.5 3.8 2.8 12.2 3.5 Texture (kg / cm2 ) 60 44 38 40 54 57 Tensile strength (kg / cm2) 420 340 300 310 390 400 Oil resistance (%) JIS # 3 2 0 2 2 3 2 Squid oil 11 4 12 12 12 11 Gasoline 23 12 22 21 26 23 -25- (Please read the notes on the back before filling this page)

本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 520379 A7 B7 五、發明説明（） 經濟部智慧財產局員工消費合作社印製 表3 實施例 11 12 13 14 15 16 (單體） 丙烯腈(份） 23 45 34 20 苯乙烯(份） 44 42 1,3-丁二烯 (份） 65 50 53 56 59 68 甲基丙烯酸 (份） 12 6 2 2 7 12 乳膠 N P Q R S Τ 抗老化劑 2,5-二- 對-甲酚 丁基化壬 N-苯基- Ν,Ν，-二- 二硫代氨 第三-醯 與二環丁 基化苯酚 N，-(l，3- 2-萘基-對 基甲酸鎳 基氫醌 二烯之丁 基化反應 生成物 二甲基丁 基）-對-苯 二胺 -苯二胺 熔點（°C) 172 115 &lt;30 44 225 85 分散方法 珠混練機 珠混練機 乳化 乳化 珠混練機 珠混練機 (浸漬模製 物之物性） 耐熱變色性 56.8 55.2 55.7 55.4 55.9 65.3 耐光變色性 52.7 50.9 51.2 50.3 51.5 60.2 耐變粉紅色 性 0.18 0.10 0.12 3.21 3.12 2.10 -26 - (請先閲讀背面之注意事項再填寫本頁)This paper size applies the Chinese National Standard (CNS) A4 specification (210X297mm) 520379 A7 B7 V. Description of the invention () Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economy 3 Table 11 Example 11 12 13 14 15 16 (single) Acrylonitrile (parts) 23 45 34 20 Styrene (parts) 44 42 1,3-butadiene (parts) 65 50 53 56 59 68 Methacrylic acid (parts) 12 6 2 2 7 12 Latex NPPRS T Anti-aging agent 2,5-di-p-cresol butylated nonyl N-phenyl-N, N, -di-dithioamino tertiary-fluorene with bicyclobutylated phenol N,-(l, 3- 2 -Naphthyl-Phenyl nickel hydroquinone diene butylation reaction product dimethylbutyl) -P-phenylenediamine-phenylenediamine Melting point (° C) 172 115 &lt; 30 44 225 85 Dispersion Method Bead Kneading Machine Bead Kneading Machine Emulsifying and Emulsifying Bead Kneading Machine (Physical properties of impregnated moldings) Heat discoloration resistance 56.8 55.2 55.7 55.4 55.9 65.3 Light discoloration resistance 52.7 50.9 51.2 50.3 51.5 60.2 Resistance to pinking 0.18 0.10 0.12 3.21 3.12 2.10 -26-(Please read the notes on the back before filling out this page)

本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）This paper size applies to China National Standard (CNS) A4 (210X 297 mm)

Claims (1)

520379520379 顧、荈:丨 ；：：Ί __ ! ^ y^'^: y'Ul ill 一一…、”，· 一，, 六、申請專利範圍 第89 1 1 2443號「浸漬模型用乳膠及浸漬模型物」專利案 (91年12月15日修正） 六、申請專利範圍： 1 . 一種浸漬模製.用乳膠，其係將48〜70重量％之由 1，3 · 丁二烯、異戊二烯、2，3 -二甲基-1 , 3 - 丁 二烯、2 -乙基-1 , 3 - 丁 二烯、1 , 3 -戊二烯及氯化戊二烯中選出之至少一種 的共軛二烯單體、2〜1 5重量％之由丙烯酸、甲基丙 烯酸、衣康酸、馬來酸、富馬酸、丁烯三羧酸、富馬 酸單丁酯、馬來酸單丁酯、馬來酸-2 -羥基丙酯、 馬來酸酐、檸康酸酐、苯乙烯磺酸、乙烯基磺酸、甲 基乙烯基磺酸、（甲基）烯丙基磺酸、（甲基）丙烯 酸一 2 —磺酸乙酯、2 —丙烯醯胺一 2 —羥基丙烷磺 酸、（甲基）丙烯酸一 3 —氯一 2 -磷酸丙酯、（甲 基）丙烯酸一 2 —磷酸乙酯、及3 —芳氧基一 2 -羥 基丙烷磷酸中選出之至少一種的乙烯性不飽和酸單 體、及20〜50重量％的含有可與此等共聚合之其他乙 烯性不飽和腈單體及/或芳香族乙烯單體予以聚合所 得的共聚物之乳膠，其特徵爲在構成乳膠之共聚物表 面上結合或吸附的酸基量與該共聚物乳膠於水相中酸 基量之合計，以鹽酸當量換算爲1克共聚物中具〇 . 1 〜2微當量。 2 ·如申請專利範圍第1項之浸漬模製用乳膠，其中乙烯 520379 六、申請專利範 圍 性 不 飽 和 腈 單 體係爲自丙烯腈、甲基丙烯腈、富 馬 腈 、 a - 氯 丙 烯 腈、及α -氰基乙基丙烯腈中選出 之 至 少 一 種 〇 3 .如 串 =主 δ円 專 利 ΪΕ 圍第1項之浸漬模製用乳膠，其中 芳 香 族 乙 烯 單 體 係 自苯乙烯、甲基苯乙烯、乙烯基甲 苯 - 氯 化 苯 乙 嫌 &gt; 及羥基甲基苯乙烯中選出之至少一: 種 〇 4 .如 串 請 專 利 範 圍第1項之浸漬模製用乳膠，其中 共 聚 物 之 乳 膠 係 Μ 〆、 有下述式（1 )所定義的化學安定性 指 數 CS 値。 1 . CS2 値、CS1 値 S 3 . 0% 5 .如 串 Ξ主 δ円 專 利 範 圍第1項之浸漬模製用乳膠，其 中 對 100 ； 重； 量. 份ΐ 膠固成分而言含有0.1〜3重量份抗 老 化 劑 所 成 〇 6 .如 串 ξ主 δ円 專 利 範 圍第5項之浸漬模製用乳膠，其中 抗 老 化 劑 係 爲 苯 酚 系抗老化劑。 7 .如 串 請 專 利 範 圍第5項之浸漬模製用乳膠，其中 抗 老 化 劑 在 常 溫 下 爲固體，且其熔點比製造浸漬模 製 物 所 使 用 的 最 高 溫度較低者。 8 .如 申 Ξ主 δ円 專 利 範 圍第5項之浸漬模製用乳膠，其中 抗 老 化 劑 係 爲 藉 由 高速珠混練機予以粉碎者。 9 .— 種 浸 漬 模 製 物，其特徵爲使如申請專利範圍第 1 項 之 浸 漬 模 製 用 乳膠浸漬模製而成。 1 0 ·如申請專利範圍第9項之浸漬模製物，其係薄 -2- 物 手 520379 六、申請專利範圍 套。 π ·如申請專利範圍第丨項之浸製模製用乳膠，其中在 構成乳膠之共聚物表面上結合或吸附的酸基量與該共 聚物乳膠於水相中酸基量之合計，以鹽酸當量換算爲 1克共聚物中具0.46〜1.51毫當量。 1 2 ·如申請專利範圍第1項之浸製模製用乳膠，其中乙 烯性不飽和酸單體係爲丙烯酸或甲基丙燃酸。 1 3 ·如申請專利範圍第1項之浸製模製用乳膠，其中乙 烯性不飽和腈單體係爲丙烯腈。 1 4 ·如申請專利範圍第1項之浸製模製用乳膠，其中芳 香族乙嫌單體係爲苯乙儲。 1 5 .如申請專利範圍第1項之浸製模製用乳膠，其中共 聚物之乳膠係將由48〜70重量％之ι，3 -丁二；)^、2〜15 重量％之丙烯酸或甲基丙烯酸、及20〜50重量％之丙烯 腈或苯乙烯所構成之單體予以聚合而得。 1 6 .如申請專利範圍第1項之浸製模製用乳膠，其中共 聚物之乳膠係將由50〜70重量％之1，3-丁二烯、2〜15 重量％之甲基丙烯酸、及20〜45重量％之丙烯腈所構成 之單體予以聚合而得。Gu, 荈: 丨; :: Ί __! ^ Y ^ '^: y'Ul ill one by one ..., ", ·, one, six, the scope of patent application 89 1 1 2443" latex for dipping models and dipping models "Patent" (revised on December 15, 91) 6. Scope of patent application: 1. A latex for dipping moulding. It uses 48 ~ 70% by weight of 1,3 butadiene, isoprene Olefin, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and chlorinated pentadiene Conjugated diene monomer, 2 to 15% by weight of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, butenetricarboxylic acid, monobutyl fumarate, maleic acid Butyl ester, 2-hydroxypropyl maleate, maleic anhydride, citraconic anhydride, styrene sulfonic acid, vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, (formaldehyde) (Meth) acrylic acid 2-ethyl sulfonate, 2-propenylamine- 2-hydroxypropane sulfonic acid, (meth) acrylic acid 3-chloro-2-propionic phosphate, (meth) acrylic acid 2- 2-ethyl phosphate Esters, and 3-aryl At least one ethylenically unsaturated acid monomer selected from oxy-2-hydroxypropane phosphoric acid, and 20 to 50% by weight of other ethylenically unsaturated nitrile monomers and / or aromatics that can be copolymerized with these The latex of a copolymer obtained by polymerizing an ethylene monomer is characterized in that the total amount of acid groups bound or adsorbed on the surface of the copolymer constituting the latex and the total amount of acid groups in the aqueous phase of the copolymer latex are converted into hydrochloric acid equivalents as 1 ～ 2 microequivalents in 1 g of copolymer. 2 · The latex for impregnation molding as described in the first item of the patent application, in which ethylene is 520379 Sixth, the patent application scope of the unsaturated nitrile single system is from acrylonitrile, methacrylonitrile, fumaronitrile, a-chloroacrylonitrile And at least one selected from α-cyanoethylacrylonitrile. For example, string = main δ 円 Patent No. 1 for the impregnation molding latex, wherein the aromatic vinyl single system is made of styrene, methyl At least one selected from styrene, vinyltoluene-chlorinated phenethyl chloride, and hydroxymethylstyrene: species 04. For example, the latex for impregnation molding of the patent scope item 1, the copolymer latex System M Μ has a chemical stability index CS 定义 defined by the following formula (1). 1. CS2 値, CS1 値 S 3. 0% 5. Such as latex for impregnation molding of the patent scope item 1 of the main δ 円, which is 100% by weight; the amount. Parts ΐ The cementation component contains 0.1 ~ 3 parts by weight of an anti-aging agent. For example, the latex for impregnation molding of item 5 of the patent scope, where the anti-aging agent is a phenol-based anti-aging agent. 7. For the latex for impregnating moulding, please refer to item 5 of the patent, where the anti-aging agent is solid at normal temperature and its melting point is lower than the highest temperature used for making impregnating mouldings. 8. The latex for impregnation molding as described in the patent No. 5 in the patent scope of item 5, where the anti-aging agent is pulverized by a high-speed bead kneader. 9 .— A dip-molding product, which is characterized in that the dip-molding as described in item 1 of the patent application scope is a dip-molding process of latex. 1 0. If the impregnated mouldings in item 9 of the scope of patent application, it is thin -2- object hand 520379 6. Application scope of patent scope. π · For the latex for infusion molding as described in the scope of the patent application, the total amount of acid groups bound or adsorbed on the surface of the copolymer constituting the latex and the total amount of acid groups in the aqueous phase of the copolymer latex is expressed as hydrochloric acid. Equivalents are 0.46 to 1.51 milliequivalents in 1 gram of copolymer. 1 2 · The latex for infusion molding according to item 1 of the scope of patent application, in which the ethylenically unsaturated acid monosystem is acrylic acid or methacrylic acid. 1 3 • The latex for infusion molding as described in item 1 of the scope of patent application, wherein the ethylenically unsaturated nitrile single system is acrylonitrile. 1 4 · If the latex for infusion molding is used in item 1 of the scope of patent application, the aromatic ethyl benzene monomer system is phenethyl storage. 15. If the latex for infusion molding of item 1 of the scope of the patent application, the latex of the copolymer will be from 48 to 70% by weight of ι, 3-butadiene; 2), 2 to 15% by weight of acrylic acid or formaldehyde It is obtained by polymerizing a monomer composed of acrylic acid and 20 to 50% by weight of acrylonitrile or styrene. 16. If the latex for infusion molding according to item 1 of the scope of patent application, the latex of the copolymer is composed of 50 to 70% by weight of 1,3-butadiene, 2 to 15% by weight of methacrylic acid, and A monomer composed of 20 to 45% by weight of acrylonitrile is polymerized.